CN117652518A - Preparation and application of emamectin benzoate polymer gel slow-release granule - Google Patents
Preparation and application of emamectin benzoate polymer gel slow-release granule Download PDFInfo
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- CN117652518A CN117652518A CN202311677303.2A CN202311677303A CN117652518A CN 117652518 A CN117652518 A CN 117652518A CN 202311677303 A CN202311677303 A CN 202311677303A CN 117652518 A CN117652518 A CN 117652518A
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- emamectin benzoate
- polymer gel
- release
- slow
- bentonite
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- CXEGAUYXQAKHKJ-NSBHKLITSA-N emamectin B1a Chemical compound C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](NC)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 CXEGAUYXQAKHKJ-NSBHKLITSA-N 0.000 title claims abstract description 179
- 229920000642 polymer Polymers 0.000 title claims abstract description 120
- 239000008187 granular material Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000007863 gel particle Substances 0.000 claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 62
- 239000000440 bentonite Substances 0.000 claims abstract description 59
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 59
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 56
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000661 sodium alginate Substances 0.000 claims abstract description 33
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 33
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 33
- 241000256251 Spodoptera frugiperda Species 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000011268 mixed slurry Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000007711 solidification Methods 0.000 claims abstract description 3
- 230000008023 solidification Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 11
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 11
- 235000005822 corn Nutrition 0.000 claims description 11
- 238000000790 scattering method Methods 0.000 claims description 2
- 241000209149 Zea Species 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 18
- 230000000857 drug effect Effects 0.000 abstract description 4
- 239000000499 gel Substances 0.000 description 89
- 229940092782 bentonite Drugs 0.000 description 49
- 238000010521 absorption reaction Methods 0.000 description 40
- 239000003814 drug Substances 0.000 description 26
- 229940079593 drug Drugs 0.000 description 21
- 238000009792 diffusion process Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 239000000575 pesticide Substances 0.000 description 13
- 238000011068 loading method Methods 0.000 description 12
- 240000008042 Zea mays Species 0.000 description 9
- 230000001186 cumulative effect Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 241000238631 Hexapoda Species 0.000 description 8
- 235000010443 alginic acid Nutrition 0.000 description 8
- 229920000615 alginic acid Polymers 0.000 description 8
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 6
- 229960001126 alginic acid Drugs 0.000 description 5
- 239000000783 alginic acid Substances 0.000 description 5
- 150000004781 alginic acids Chemical class 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000013268 sustained release Methods 0.000 description 4
- 239000012730 sustained-release form Substances 0.000 description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229940072056 alginate Drugs 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- RGNPBRKPHBKNKX-UHFFFAOYSA-N hexaflumuron Chemical compound C1=C(Cl)C(OC(F)(F)C(F)F)=C(Cl)C=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F RGNPBRKPHBKNKX-UHFFFAOYSA-N 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229940080314 sodium bentonite Drugs 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002552 dosage form Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 208000003643 Callosities Diseases 0.000 description 1
- 241001057636 Dracaena deremensis Species 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241001477931 Mythimna unipuncta Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- ORJVYWIAEOVIRD-UHFFFAOYSA-N acetonitrile azane methanol Chemical compound N.OC.CC#N ORJVYWIAEOVIRD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003640 drug residue Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a preparation method of emamectin benzoate polymer gel slow-release granules, which comprises the following steps: firstly, dissolving sodium alginate in deionized water, then adding bentonite and emamectin benzoate raw material, and continuously stirring to form uniform mixed slurry; dropwise adding the mixed slurry into a calcium chloride solution for solidification, and filtering to obtain gel particles; washing calcium ions on the surfaces of the gel particles with deionized water, and fully drying at 45 ℃ to obtain emamectin benzoate polymer gel slow-release granules; the invention also discloses application of the emamectin benzoate polymer gel slow-release granule in preventing and controlling spodoptera frugiperda; the emamectin benzoate polymer gel slow-release granule prepared by the invention has obvious control effect on spodoptera frugiperda, can achieve ideal drug effect release, can prepare granules with different particle sizes according to the field requirement, and can also selectively prepare granules with different bentonite contents according to the residence time of spodoptera frugiperda.
Description
Technical Field
The invention relates to the technical field of pesticides. In particular to a preparation method and application of emamectin benzoate polymer gel slow release granules.
Background
Spodoptera frugiperda is also called autumn armyworm, belongs to lepidoptera night moth family, mainly endangers crops such as corn, sugarcane, sorghum and the like, and because spodoptera frugiperda prefers to eat tender leaves, the corn endanger period is mainly in a seedling stage to a large horn mouth stage, the damage of corn after heading is less, and spodoptera frugiperda can be prevented and treated by using emamectin benzoate.
Emamectin benzoate (emamectin benzoate) is used as a biological insecticidal acaricide, and has the characteristics of broad insecticidal spectrum, good effect, low toxicity (the preparation is nearly nontoxic), low residue, no public hazard and the like, and is deeply favored by vast growers in recent years. The emamectin benzoate has six dosage forms, namely emulsifiable concentrates, aqueous emulsion, microemulsion, suspending agents, water dispersible granules and soluble granules, and the emamectin benzoate is prepared into liquid for application by adopting the dosage forms, but the emamectin benzoate is easy to decompose under illumination, so that the emamectin benzoate is easy to decompose when being applied, and the emamectin benzoate is difficult to exert the original efficacy, so that repeated application is needed to make up in practice, the pesticide cost is increased, and the environment is possibly polluted. The defects can be effectively overcome if the emamectin benzoate can be processed into a slow-release type preparation.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide the preparation and the application of the emamectin benzoate polymer gel slow-release granule, wherein the emamectin benzoate polymer gel slow-release granule has high emamectin benzoate drug loading rate and prolongs the duration of pesticide.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of emamectin benzoate polymer gel slow-release granules comprises the following steps:
(1) Firstly, dissolving sodium alginate in deionized water, then adding bentonite and emamectin benzoate raw material, and continuously stirring to form uniform mixed slurry;
(2) Dropwise adding the mixed slurry into a calcium chloride solution for solidification, and then filtering to obtain gel particles;
(3) And (3) washing calcium ions on the surfaces of the gel particles by deionized water, and fully drying at 45 ℃ to obtain the emamectin benzoate polymer gel slow-release granule. The low-temperature drying at 45 ℃ can avoid influencing the effective components.
In the preparation method of the emamectin benzoate polymer gel slow-release granule, in the step (1), sodium alginate: bentonite: emamectin benzoate: the proportion of deionized water is (1.26-1.80): (0.09-0.54): 0.2:98.0.
the preparation method of the emamectin benzoate polymer gel slow-release granule comprises the following steps of: bentonite: emamectin benzoate: deionized water is present in a ratio of 1.71:0.09:0.2:98, or 1.62:0.18:0.2:98, or 1.44:0.36:0.2:98, or 1.26:0.54:0.2:98.
In the step (2), the mixed slurry is dripped into 0.5M calcium chloride solution to be solidified for 50min. The gel cannot be formed by dripping the gel into other calcium salts.
In the step (2), the mixed slurry is dripped into a syringe, the inner diameter of the water outlet of the syringe is 0.91-1.69mm, and the dripping speed is 9-13mL min -1 . The particle size of the emamectin benzoate polymer gel slow-release granule can be controlled by adjusting the inner diameter and the dropping speed of the water outlet.
In the preparation method of the emamectin benzoate polymer gel slow-release granule, in the step (3), the dried emamectin benzoate polymer gel slow-release granule is spherical, and the particle size is 0.90mm-1.7mm.
The preparation method of the emamectin benzoate polymer gel slow-release granule,
(1) Firstly, dissolving sodium alginate in deionized water, then adding bentonite and emamectin benzoate raw material, and continuously stirring to form uniform mixed slurry; sodium alginate: bentonite: emamectin benzoate: the proportion of deionized water is (1.26-1.80): (0.09-0.54): 0.2:98.0;
(2) Dropwise adding the mixed slurry into 0.5M calcium chloride solution by using a syringe, solidifying for 50min, and filtering to obtain gel particles; dripping the mixed slurry by using a syringe, wherein the inner diameter of a water outlet of the syringe is 0.91-1.69mm, and the dripping speed is 9-13 mL/min -1 ；
(3) And (3) washing calcium ions on the surfaces of the gel particles by deionized water, and fully drying at 45 ℃ to obtain the emamectin benzoate polymer gel slow-release granule.
The emamectin benzoate polymer gel slow-release granule is applied to the control of spodoptera frugiperda of corn.
The application of the emamectin benzoate polymer gel slow-release granule adopts a granule scattering method to apply the emamectin benzoate polymer gel slow-release granule.
The application of the emamectin benzoate polymer gel slow-release granule is that the emamectin benzoate polymer gel slow-release granule is applied to a horn mouth of corn, and the application amount is 3kg/ha-7.5kg/ha.
The technical scheme of the invention has the following beneficial technical effects:
according to the preparation method, the addition amount of sodium alginate and bentonite is adjusted, and the hydrogel with a shell-core structure is prepared by using a multivalent cation crosslinking method, so that the emamectin benzoate raw drug package is embedded into the sodium alginate gel. The surface of the dried gel has a large number of gaps, the gaps are gradually reduced along with the addition of the bentonite content, and the gaps are also reduced, so that the addition of the bentonite reduces the permeability of the sodium alginate gel, changes the morphology of the sodium alginate gel, increases the diffusion distance of the emamectin benzoate molecules from gel particles, and can realize the slow release purpose of the emamectin benzoate polymer gel slow release granules.
Firstly adding sodium alginate, and then adding bentonite and emamectin benzoate, so that the emamectin benzoate can be smoothly embedded into sodium alginate gel, and the preparation efficiency of emamectin benzoate polymer gel particles is improved. The bentonite changes the permeability and morphology of the sodium alginate gel, so that the encapsulation rate of the emamectin benzoate polymer gel granule is improved.
If the three components are mixed at the same time, or the emamectin benzoate raw medicine is dissolved first, and then the sodium alginate and the bentonite are added, the bentonite can block the sodium alginate in advance, and the emamectin benzoate raw medicine does not enter into a gap of the sodium alginate, so that the medicine carrying capacity of the emamectin benzoate polymer gel slow-release granule is greatly reduced.
The emamectin benzoate polymer gel slow-release granule prepared by the invention can achieve ideal drug effect release, can be prepared into granules with different particle sizes according to the field requirements, and can be prepared into granules with different bentonite contents according to the residence time of spodoptera frugiperda;
the emamectin benzoate polymer gel slow release granule prepared by the invention has obvious control effect on spodoptera frugiperda; the emamectin benzoate is in gaps of the polymer granules, so that the release speed of the emamectin benzoate can be obviously reduced, the duration of the pesticide is prolonged, and the granules with larger particle size have longer duration of the pesticide;
the bentonite and the sodium alginate are both environment-friendly materials, the residue of the emamectin benzoate in the emamectin benzoate polymer gel slow-release granule after release has no environmental pollution, and besides the emamectin benzoate is applied to the control of spodoptera frugiperda of corn, the emamectin benzoate is used as a broad-spectrum insecticidal and Sha Man agent, so that the emamectin benzoate polymer gel slow-release granule can also be used for the control of other pests and has wide application.
Drawings
FIG. 1 is a schematic process diagram of a preparation method according to an embodiment of the present invention;
FIG. 2 is an optical photograph of emamectin benzoate polymer gel particles before and after drying; (a) before drying and (b) after drying;
FIG. 3 is an infrared spectrum of emamectin benzoate, sodium alginate, bentonite and emamectin benzoate polymer gel particles;
FIG. 4 shows the apparent morphology of polymer gel particles with different contents of sodium alginate and bentonite, which are observed by a scanning electron microscope;
FIG. 5 is a graph showing the release process of alluring red from polymeric gel particles;
FIG. 6 is a graph of polymer gel particles measured by a three-dimensional microscope with super depth of field;
FIG. 7 is a graph showing the water absorption kinetics of the polymer gel particles;
FIG. 8 is a graph of the water absorption kinetics of gel particles of different particle size;
FIG. 9 is an SEM image of the polymer gel particles before and after water absorption;
FIG. 10 is a graph showing the cumulative release profile of emamectin benzoate from polymeric gel particles;
FIG. 11 is a graph showing cumulative release profiles of emamectin benzoate from polymer gel particles of different particle sizes;
FIG. 12 is a graph showing the cumulative release profile of emamectin benzoate polymer granules at various water levels.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
1. Preparation of emamectin benzoate polymer gel granule
The invention provides a preparation method of emamectin benzoate polymer gel sustained-release granules, and the preparation method is shown in fig. 1 as a preparation flow chart.
Accurately weighing corresponding sodium alginate (A) according to the table 1, adding deionized water, placing on a magnetic stirrer, stirring at normal temperature until the sodium alginate is completely dissolved, adding bentonite (B) and emamectin benzoate crude drug (E), and continuously stirring to form uniform mixed slurry;
the slurry was added dropwise to 0.5M CaCl using a syringe 2 Solidifying in the solution for 50min; the mixed slurry was added dropwise with a syringe, the injectionThe inner diameter of the water outlet of the device is 0.91-1.69mm, and the dropping speed is 9-13mL min -1 ；
Filtering the obtained gel particles, washing calcium ions on the surface by deionized water, and fully drying in a 45 ℃ electrothermal blowing drying oven to obtain the emamectin benzoate polymer gel slow-release granule.
Reagent: emamectin benzoate as a bulk drug (Hubei Kang Baotai fine chemical Co., ltd.); 5% emamectin benzoate (Hebei Xingbai agricultural technologies Co., ltd.); sodium alginate, anhydrous calcium chloride (national pharmaceutical group chemical reagent, liability company); bentonite (the institute of optical and complex fine UI in the Tianjin city); methanol more than or equal to 99.9%, acetonitrile more than or equal to 99.9% (Anhui Tiandi high purity solvent Co., ltd.).
The obtained emamectin benzoate polymer gel slow release granules are respectively named as EABx, wherein x is the approximate number of the weight percentages of bentonite, bentonite and sodium alginate in the base material, and EA is a control group which does not contain bentonite and only contains sodium alginate (A) and emamectin benzoate crude drug (E).
TABLE 1 Emamectin benzoate Polymer gel granule configuration Table
2. The structure of the emamectin benzoate polymer gel slow-release granule is characterized by a Fourier transform infrared spectrum (FTIR spectrum), a scanning electron microscope and a super depth of field three-dimensional microscope, and the test and analysis of the drug loading rate, the water absorption rate and the indoor release test are carried out to obtain the characteristics of the emamectin benzoate polymer gel slow-release granule so as to facilitate the theoretical guidance of application.
2.1 FTIR Spectroscopy
The infrared spectrum (FTIR spectrum) was measured by using a total reflection attenuated Fourier transform infrared spectrometer of US ThermoFisher Nicolet, and the scanning range was 650-4000cm -1 Resolution of 4cm -1 The scanning times are accumulated for 10 times, the measured results are shown in figure 3, wherein B represents the infrared spectrogram of bentonite, A represents the infrared spectrogram of sodium alginate, E represents the infrared spectrogram of emamectin benzoate, and EAB 30 Represents EAB 30 Infrared spectrogram of emamectin benzoate polymer gel slow-release granule of experimental group;
2.2、SEM
the gel granules are adhered on a stage by a dry method, surface metal spraying treatment is carried out by using a TRP450 magnetron sputtering coating system, and the surface morphology is analyzed by using a Japanese SU5000 scanning electron microscope.
2.3, super depth of field three-dimensional microscope
The method for preparing the emamectin benzoate polymer gel slow release granule in the first step is adopted to prepare the tempting red marked polymer granule. And (3) observing the release process of the induced red granules in water by using a VHX-5000 type super depth of field three-dimensional microscope, and measuring the particle size of the emamectin benzoate polymer gel granules.
2.4 measurement of drug loading Rate
Accurately weighing 0.500g of emamectin benzoate polymer gel slow release granule, placing into a volumetric flask, adding a proper amount of methanol, performing ultrasonic treatment in an ultrasonic cleaner under a normal temperature 40Hz environment for 2 hours, completely dissolving the emamectin benzoate, fixing the volume to 50mL by using the methanol, filtering by using an organic film with the thickness of 0.22 mu m, and filling into a 1.5mL light-resistant sample injection bottle. And (3) measuring the effective content of emamectin benzoate in the filtrate by adopting a high performance liquid chromatography external standard method. The mobile phase was methanol-acetonitrile-ammonia (ammonia: water=1:300) =42: 42:16; the flow rate was 1.5 mL/min -1 The method comprises the steps of carrying out a first treatment on the surface of the C18 chromatographic column with column temperature of 30deg.C; the detection wavelength is 245nm; the sample loading was 5. Mu.L.
LC(％)＝M1/M2×100
Wherein LC (%) is the drug loading rate of the polymer granules, M1 is the content of emamectin benzoate in the polymer gel slow release granules of the emamectin benzoate, and M2 is the mass of the polymer gel slow release granules of the emamectin benzoate.
2.5 Water absorption kinetics
About 0.2g of sodium alginate-bentonite blank particles are weighed, placed in a culture dish, added with a proper amount of deionized water at normal temperature, taken out at a preset time point, the water on the surface is sucked by filter paper, the water absorption of the particles is measured by a weighing method, and the water absorption rate is calculated according to the following formula. Under the same conditions, 3 parallel tests were carried out, and the average value was obtained.
Wherein Wt is the mass of the granule after water absorption at time t, and Wi is the initial mass of the granule.
2.6 release experiments of Polymer gel particles
1.0g of emamectin benzoate polymer gel slow release granule is weighed into a 200mL conical flask, 100mL of methanol water (methanol: water=30:70) is added, and the mixture is oscillated at a speed of 150r/min in a constant temperature oscillator at 25+/-1 ℃. 1mL of the solution was taken out at the set time point, 1mL of methanol water was added additionally, and the time was set to 0.5h, 1.0h, 2.0h, 4.0h, 7.0h, 11.0h, 24.0h, 31.0h, 48.0h, 55.0h, and the released curves of emamectin benzoate were calculated by measuring the emamectin benzoate content by HPLC according to the following formula after the filtration of the taken out samples.
Wherein Er is the cumulative emamectin benzoate release (%) relative to the pesticide loading; ve is (ve=1.0 mL) sample volume; c (C) n (mg/mL) is the emamectin benzoate concentration in the release medium at time n; v (V) 0 Is the volume of release medium (200 mL); m is M E (mg) is the total amount of the pesticide trapped in the emamectin benzoate polymer gel slow release granule. The measurement was repeated 3 times.
3. Results and analysis
3.1 measurement of drug loading Rate
The emamectin benzoate polymer gel slow-release granules with three particle sizes, of which the bentonite content and the alginic acid content are changed in series, are prepared through experiments, the obtained composite gel particles are approximately spherical as shown in figure 2, the particle size of small particles in the dried emamectin benzoate gel particles is about 0.95mm, the particle size of medium particles is about 1.37mm, and the particle size of large particles is about 1.60mm.
The emamectin benzoate content and the encapsulation efficiency in the emamectin benzoate polymer gel slow release granule are shown in the emamectin benzoate content data at the right end of the table 1.
3.2、FTIR
As shown in fig. 3, the characteristic peaks of the emamectin benzoate crude drug (E) are: 3453cm -1 The position is a stretching vibration peak of O-H bond, 2965cm -1 At saturated C-H cm -1 Key stretching vibration peak, 1733cm -1 A stretching vibration peak of C=O bond at 1596cm -1 The vicinity of the position is a telescopic vibration peak of benzene ring skeleton, 1555cm -1 Bending vibration peak of N-H bond 1448cm -1 The peak of asymmetric bending vibration of C-H bond is 1376cm -1 The C-H bond symmetrical bending vibration peak is shown. Sodium alginate (A) except at 3365 and 1028cm -1 Near the absorption of O-H stretching vibration and C-H bending vibration, 1600 cm and 1430cm -1 Obvious symmetrical and asymmetrical telescopic vibration characteristic absorption of carboxyl C=O bonds appears nearby. Bentonite (B) except at 3631 and 1643cm -1 The vicinity of which is 1029cm apart from the stretching vibration and the bending vibration of the structure OH -1 Characteristic absorption of Si-O bond stretching vibration occurs and is between 3500 and 3300cm -1 Broad peak absorption of adsorbed water molecules occurs in the wavelength range;
emamectin benzoate polymer gel slow release granule (EAB) 30 ) 3353cm appear in -1 、2965cm -1 And 2933cm -1 Characteristic peaks of emamectin benzoate, which indicate that emamectin benzoate is loaded into the granule; bentonite as modified material of granule with characteristic peak 3612cm -1 、3543cm -1 And 1643cm -1 Etc. are also present in the granules, indicating that bentonite is well dispersed in the granules.
3.3、SEM.
As shown in fig. 4, the surface morphology of the carrier material has a very important effect on pesticide release; the interaction between bentonite and alginic acid may change the surface morphology of the polymer gel and affect the release behaviour of pesticides, and in addition, emamectin benzoate is slightly soluble in water and encapsulation in the gel may also affect the morphology of the gel particles, so that the surface morphology of the particles observed by a Scanning Electron Microscope (SEM) in the use of the invention. As can be seen from fig. 4, the surface of the emamectin benzoate polymer gel particles without bentonite has a large number of cracks, the cracks on the surface of the gel particles gradually decrease with the increase of the bentonite content, and even the surface appearance is uniform and nearly compact when the bentonite addition amount is 20% -30%, because the bentonite plays a certain cross-linking role in the super-absorbent composite network; as the bentonite content increases, the crosslink density of the composite increases, resulting in a decrease in gel porosity.
3.4, super depth of field three-dimensional microscope
To understand the release process of emamectin benzoate from polymer gel particles, the process of inducing red release in the gel particles was observed with a super depth of field three-dimensional microscope. Fig. 5 is a view of a video of the release of allure red recorded by a three-dimensional microscope with super depth of field, the left, middle and right images in fig. 5 are respectively state diagrams of the allure red in the experimental polymer gel particles placed in water, which are respectively in the state of diffusion for 32 seconds, 2 minutes and 33 seconds and 2 minutes and 50 seconds, from which it can be seen that the color of the allure red gel particles becomes lighter with time, SEM analysis shows that the gel particles have a large number of gaps, so that the allure red release in water is a process of diffusing into water through the gaps of the gel particles, and fig. 5 shows that the allure red around the gel particles tends to diffuse to the surroundings with the increase of time, and the color becomes lighter from the original, which is a result of the allure red diffusing out of the gel particles to be accumulated around the gel particles and diffusing into the surrounding water due to the concentration difference.
Fig. 6 is a photograph of polymer gel particles of emamectin benzoate particles measured by a three-dimensional microscope with super depth of field, and the particles with small, medium and large particle diameters are sequentially shown from left to right in fig. 6, and it can be seen from the photograph that the gel particle diameter of the small particles is about 0.95mm, the gel particle diameter of the medium particles is about 1.37mm, and the gel particle diameter of the large particles is about 1.60mm.
3.5 Water absorption kinetics
The water absorption-time change curve of emamectin benzoate polymer gel particles is shown in figure 7. From the figure, it can be seen that the water absorption of the polymer gel particles increases rapidly and then decreases slowly. As shown in FIG. 7, the alginate-bentonite polymer gel particles can quickly absorb water, and the water absorption reaches equilibrium basically in 40min, and the water absorption rate is less than 20%. Alginate has a large number of hydrophilic groups, is easily swelled in water, and is hydrophilic, so the internal chemical structure of the polymer gel interacts with electrolytes or other molecules in solution, thereby affecting the water absorption of the granules. But the addition of bentonite can improve the compactness of the alginate-bentonite polymer gel particles, and meanwhile, the bentonite also contains hydroxyl groups, so that hydrogen bonds can be formed with the alginate, and further expansion of the particles is effectively inhibited. It can also be seen that bentonite can improve the hydrophobicity of the particles and inhibit the water absorption of the particles, so that the water absorption inhibiting effect of the particles is more remarkable. In addition, bentonite also contains ammonium groups, which can form-O-H-N type hydrogen bonds with alginate and can inhibit the expansion of particles.
SEM images showed that the gel had a large number of gaps. During the water absorption process, a large amount of water enters the gel through these gaps and fills them. Diffusion of the active compound in the polymer gel is promoted because a large amount of water penetrates the hydrogel matrix and is displaced within the matrix.
The water swelling of the polymer gel particles is a rapid process and gradually approaches equilibrium after 40 min. Bentonite has a weaker affinity for water than alginic acid, and at the same time, the interaction between bentonite and alginic acid prevents the swelling of the alginic acid gel by water absorption. With the addition of bentonite from 0-30%, the porosity of the polymer gel particles gradually decreases and tends to be compact (SEM), further resulting in a decrease in the water absorption of the gel particles.
The results of the experiments of the water absorption kinetics of the granules with different particle sizes are summarized in fig. 8, the change rule of the experiments is similar to that of fig. 7, and the water absorption rate of the granules with three particle sizes is rapidly increased and then slowly reduced. When the water absorption reaches the final balance, the particle size of the polymer gel particles obviously influences the water absorption. The equilibrium water absorption rates of the large particles, the medium particles and the small particles are respectively 16%, 12% and 2%, the swelling rate is closely related to the particle size of the polymer gel, and from SEM analysis, the gel has a large number of cracks, and a large amount of water enters the gel through the cracks in the water absorption process and fills the cracks, so that the smaller the particle size is, the smaller the cracks are, the less water the particles can contain, and the smaller the particle size is, thus corresponding to the following release test results of the emamectin benzoate polymer gel particles with different particle sizes.
The particle diameters of the dried particles before and after water absorption and the drug loading rates before and after water absorption of the polymer gel particles are shown in tables 2 and 3, respectively. As can be seen from the table, the particle size and the drug loading rate of the particles of the five formulations are obviously reduced after water absorption and drying, because a large amount of water is soaked into the gel from gaps on the surface of the particles in the water absorption process so that sodium ions in sodium alginate molecules in the gel are dissociated into water, and on the other hand, the obvious reduction of the drug loading rate indicates that the pesticide loss in the particles also affects the particle size after the particles are dried. This also explains that the water absorption kinetics of the granules show a slow decrease until equilibrium after the granules initially absorb water rapidly, since the granules themselves are losing their composition at the same time as they absorb water.
TABLE 2 Polymer gel particles dried particle diameter/mm before and after water absorption
TABLE 3 drug loading rate/%before and after water absorption of Polymer gel particles
FIG. 9 is a scanning electron microscope image of the polymer gel particles before and after water absorption. From the figure, the gaps on the surface of the polymer gel particles are increased after water absorption, because most of the emamectin benzoate wrapped in the particles is released during the water absorption process, and gaps are formed at the positions originally carrying the emamectin benzoate. On the other hand, in the water absorption process, the particle size of the polymer gel particles is reduced because sodium ions in sodium alginate molecules in the gel particles are dissociated into water, so that gaps on the surfaces of the gel particles after water absorption are increased.
3.6 Emamectin benzoate Release
The cumulative release profile of emamectin benzoate from the polymeric gel particles is shown in figure 10. As can be seen from the figure, emamectin benzoate as a raw medicine under the same conditions(control) and commercial drug (commodity medicine) were completely released in a very short period of time with 50% of the time T50 value of about 0.34h, whereas the release of emamectin benzoate from the gel particles was significantly slowed, with 50% of the time T50 value from the gel particles without bentonite addition increased to 4.49h, with a small amount of bentonite addition, the emamectin benzoate release 50% of the T50 value increased significantly, with increasing bentonite content within 55h of the experiment, with sample EAB 10 、EAB 20 And EAB (EAB) 30 Less than 50% and the greater the bentonite content the less the cumulative release over the same time. The results of the three-dimensional microscope observation of the super depth of field show that the emamectin benzoate is released through gaps of gel particles, while the results of the SEM image show that the gap rate of the gel particles is reduced along with the increase of the bentonite content, and even the bentonite tends to be compact when the bentonite addition amount reaches 30%, so that the accumulated emamectin benzoate release rate is smaller when the bentonite content is more, which is consistent with the results of the emamectin benzoate release test, in the same time.
In addition, in order to understand the release property of the emamectin benzoate particles, the Korsmeyer-Peppas equation is also applied to the characteristic study of the emamectin benzoate polymer gel slow release particles to fit the emamectin benzoate release data:
M t /M 0 ＝kt n
wherein M is t /M 0 The drug release rate at time t, k, and n are constants, and the fitting results are summarized in table 4. The diffusion coefficient n is the basis for analyzing the drug release mechanism, when n is not more than 0.45 and is Fickian diffusion, n is not less than 0.45 and not more than 0.89 and is the combined action of various mass transfer mechanisms (skeleton erosion, drug diffusion and the like), n is not less than 0.89 and is the relaxation drug release, and the diffusion coefficient n is controlled by the dynamics of the structural change of the polymer; the n values of the planar, cylindrical and spherical systems released according to the Fickian diffusion mechanism are respectively 0.5, 0.45 and 0.43, and the n values released according to the "Case II" transport mechanism are respectively 1.0, 0.89 and 0.85.
TABLE 4 Korsmeyer-Peppas equation and Higuch fitting results for the release of emamectin benzoate from Polymer gels
As can be seen from the results of table 4, the diffusion index n of the emamectin benzoate released from the particles is between 0.23 and 0.35, indicating that the release mechanism of emamectin benzoate is Fickian diffusion; from the results of the super depth of field three-dimensional microscope observation (fig. 5), it is known that adding the gel particles loaded with allure red to water induces the allure red to diffuse from the gel particles into the water, which is consistent with the fitting analysis results; since emamectin benzoate is slightly soluble in water, diffusion through the substrate can be considered a rate controlling step for emamectin benzoate release; the release rate of the emamectin benzoate from the polymer gel particles can be controlled by changing the size of the emamectin benzoate polymer gel slow release granule or the content of bentonite and sodium alginate.
The cumulative release profile of emamectin benzoate from granules of different particle sizes is shown in figure 11, where the larger the particle size of the same sample, the less cumulative release occurs over the same time period. Fig. 11 shows that the release rate of emamectin benzoate from the granules gradually decreases with time, because the distance of emamectin benzoate from the granules to the release medium increases towards the centre of the granules as the release process proceeds. The ultra-depth-of-field three-dimensional microscope experiment shows that the release of the emamectin benzoate is diffused through the pores of the gel particles, so that the longer the particle size is, the longer the path of the emamectin benzoate is diffused into a release medium through the pores, the more time is needed, and the gel particles with the larger particle size can prolong the duration of the pesticide; for the invention, the emamectin benzoate gel granule with proper size can be prepared according to the life habit, the growth cycle and the climate condition of spodoptera frugiperda so as to control the release effect of the emamectin benzoate and achieve the expected killing effect of the spodoptera frugiperda.
In order to examine the release condition of the emamectin benzoate polymer gel slow release granule in water, release experiments under different water contents are also carried out on the emamectin benzoate polymer gel slow release granule, specifically, the release experiments are carried out under the condition that the water content in methanol water is 2g, 4g or 6g, so as to obtain a cumulative release curve of the emamectin benzoate polymer gel slow release granule in the methanol water of 2g, 4g or 6g from the seat to the right in fig. 12. As can be seen from fig. 12, the diffusion index n of the emamectin benzoate released from the polymer gel particles at the methanol water addition amount of 2g is between 0.64 and 0.72, which belongs to non-Fickian diffusion, in which case, the release of the emamectin benzoate from the particles is co-acted by various mass transfer mechanisms including diffusion-erosion, pesticide diffusion and the like. However, when the water content of methanol is 4g or 6g, the diffusion index n is between 0.18 and 0.37 and is mainly released by Fickian diffusion. This means that in practical application, the emamectin benzoate polymer gel slow-release granule is placed in the horn mouth of corn, and the emamectin benzoate release time can be effectively prolonged under the condition of no water.
TABLE 5 Korsmeyer-Peppas and Higuchi fitting results of Emamectin benzoate Polymer gel granules released in 2g MeOH Water
TABLE 6 Korsmeyer-Peppas and Higuchi fitting results of Emamectin benzoate Polymer gel granules released in 4g methanol Water
TABLE 7 Korsmeyer-Peppas and Higuchi fitting results of emamectin benzoate Polymer gel granules in 6g MeOH Water Release
3.7, the slow release granules of emamectin benzoate have field control effect on spodoptera frugiperda
Field test example
In order to understand the control effect of the emamectin benzoate polymer gel slow-release granule on spodoptera frugiperda, field experiments are carried out on the prepared emamectin benzoate polymer gel slow-release granule. Corn variety Qian glutinous 938, 6m×5m plots were experimentally selected, 30m per cell 2 Each of which is provided withThe water and fertilizer management of the communities is the same, a land block with serious spodoptera frugiperda is selected as a test land block, and the corn plants are in the seedling growth stage and adopt a granule scattering and pesticide application method. 3 treatments and 1 blank control were set for each agent, the test was repeated 4 times with dosages of 3kg/ha, 4.5kg/ha and 7.5kg/ha, respectively, and the control group (CK) was a clear water treatment. Insect population densities were investigated prior to slow release particle application. The larvae numbers of each cell were investigated and recorded using a general survey method. The number of live larvae was recorded after 1d, 3d, 5d, 7d, 14 d. The calculation formulas of the control effect and the rate of reduction of insect population are as follows. The results of the field trials are summarized in table 8.
The rate of reduction of insect population (%) = [ (number of insect population before treatment-number of insect population after treatment)/number of insect population before treatment ] ×100
Control effect (%) = [ (treatment area reduction rate-control area reduction rate)/(1-control area reduction rate) ×100
As can be seen from Table 8, the slow release granules of emamectin benzoate polymer gel have basically high rate of reduction of insect population of 94.7-100.00% after 1 day, 3 days and 7 days, the average control effect reaches 95.8-100.00%, the reduction of insect population reaches 73.1-80.0% after 21 days, and the average control effect is 78.3-82.86%; from the results, the prepared emamectin benzoate polymer gel slow-release granule has longer lasting period, and the emamectin benzoate granule prepared by the invention has obvious control effect on spodoptera frugiperda.
Table 8 control of Spodoptera frugiperda by Emamectin benzoate Polymer gel sustained release granules
(the application amount is calculated according to the content of the effective components, 11% emamectin benzoate, the original drug content of the hexaflumuron is high, and the application amount is small.)
After the first day after administration, 11% emamectin benzoate, hexaflumuron and the granules have equivalent reduction rate and prevention and control effects, but as the emamectin benzoate polymer gel slow release granules have good controlled release effect, the sustained control effect on spodoptera frugiperda is shown, and the control effect of 11% emamectin benzoate, hexaflumuron on spodoptera frugiperda is obviously weakened from the 3 rd day.
3.8 conclusion and discussion
After the preparation of the emamectin benzoate sustained-release gel is finished, the content of the emamectin benzoate in the gel is calculated to be 35.7-46.6 mg.g through the measurement of the drug loading rate of the sustained-release gel -1 . The structure of the emamectin benzoate polymer gel slow release granule can be characterized by a Fourier transform infrared spectrum (FTIR), a Scanning Electron Microscope (SEM) and a super depth of field three-dimensional microscope, an indoor release test is analyzed, the emamectin benzoate polymer gel slow release granule can achieve ideal drug effect release, granules with different particle sizes can be prepared according to field requirements, and in addition, slow release gels with different bentonite contents can be prepared according to the residence time of spodoptera frugiperda. The ideal drug effect release can be achieved through the release performance measurement, and in the preparation process, the calcium ions on the surface are washed by deionized water before being dried after being solidified into slow release gel, so that the calcium ions are prevented from generating an essential effect on corns when being heated by water in the field application process; however, whether the crop is harmful during the field application process and whether the drug residue exists needs further research.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While the obvious variations or modifications which are extended therefrom remain within the scope of the claims of this patent application.
Claims (10)
1. The preparation method of the emamectin benzoate polymer gel slow-release granule is characterized by comprising the following steps of:
(1) Firstly, dissolving sodium alginate in deionized water, then adding bentonite and emamectin benzoate raw material, and continuously stirring to form uniform mixed slurry;
(2) Dropwise adding the mixed slurry into a calcium chloride solution for solidification, and then filtering to obtain gel particles;
(3) And (3) washing calcium ions on the surfaces of the gel particles by deionized water, and fully drying at 45 ℃ to obtain the emamectin benzoate polymer gel slow-release granule.
2. The method for preparing emamectin benzoate polymer gel slow release granules according to claim 1, wherein in the step (1), sodium alginate: bentonite: emamectin benzoate: the proportion of deionized water is (1.26-1.80): (0.09-0.54): 0.2:98.0.
3. the method for preparing emamectin benzoate polymer gel slow release granules according to claim 2, wherein in the step (1), sodium alginate is as follows: bentonite: emamectin benzoate: deionized water is present in a ratio of 1.71:0.09:0.2:98, or 1.62:0.18:0.2:98, or 1.44:0.36:0.2:98, or 1.26:0.54:0.2:98.
4. The method for preparing emamectin benzoate polymer gel slow-release granules according to claim 1, wherein in the step (2), the mixed slurry is dripped into 0.5M calcium chloride solution to be solidified for 50min.
5. The method for preparing emamectin benzoate polymer gel slow-release granules according to claim 1, wherein in the step (2), a syringe is adopted to drop the mixed slurry, the inner diameter of a water outlet of the syringe is 0.91-1.69mm, and the dropping speed is 9-13mL min -1 。
6. The method for preparing emamectin benzoate polymer gel slow-release granules according to claim 1, wherein in the step (3), the dried emamectin benzoate polymer gel slow-release granules are spherical and have the particle size of 0.90mm-1.7mm.
7. The method for preparing emamectin benzoate polymer gel slow release granules according to claim 1, which is characterized in that,
(1) Firstly, dissolving sodium alginate in deionized water, then adding bentonite and emamectin benzoate raw material, and continuously stirring to form uniform mixed slurry; sodium alginate: bentonite: emamectin benzoate: the proportion of deionized water is (1.26-1.80): (0.09-0.54): 0.2:98.0;
(2) Dropwise adding the mixed slurry into 0.5M calcium chloride solution by using a syringe, solidifying for 50min, and filtering to obtain gel particles; dripping the mixed slurry by using a syringe, wherein the inner diameter of a water outlet of the syringe is 0.91-1.69mm, and the dripping speed is 9-13 mL/min -1 ；
(3) And (3) washing calcium ions on the surfaces of the gel particles by deionized water, and fully drying at 45 ℃ to obtain the emamectin benzoate polymer gel slow-release granule.
8. The application of the emamectin benzoate polymer gel slow-release granule is characterized in that the emamectin benzoate polymer gel slow-release granule prepared by the method of claims 1 to 7 is applied to the control of spodoptera frugiperda of corn.
9. The use of the emamectin benzoate polymer gel slow release granule according to claim 8, which is characterized in that the emamectin benzoate polymer gel slow release granule is applied by adopting a granule scattering method.
10. The use of emamectin benzoate polymer gel slow release granule according to claim 9, wherein the emamectin benzoate polymer gel slow release granule is applied in a horn mouth of corn, and the application amount is 3kg/ha-7.5kg/ha.
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